3, 5-dimethyl-4-methylmercaptophenyl n-methyl carbamate and methods for combating insects



United States Patent F 12 Claims. (Cl. 167--30) The present invention isa division of copending application Ser. No. 72,306, filed Nov. 29,1960.

The present invention relates to and has as its objects new and usefulinsecticidal agents, the processes for their production and the usethereof. The new compounds of this invention are carbamates of thefollowing general formula:

Rg-X-Y-Aryl-O-G-N O(S)\R1 wherein R and R stand for hydrogen or alkylradicals, R stands for an optional alkyl radical, Y stands for CH or adirect bond between R and Y and X may be S, S0 or S0 The new compoundsin accordance with the present invention can be produced in a mannerknown in principle. For example, suitable phenols may be converted bymeans of phosgene or thiophosgene into the corresponding chloroformicacid esters or chlorothioformic acid esters and the latter reacted withammonia, or suitable primary or secondary amines.

Furthermore, suitable phenols may sometimes be reacted advantageouslywith suitable dialkylor dialkyl (-thio)carbamic acid chlorides. Ifmonoalky-lamides are to be produced, suitable phenols may also bereacted with suitable isocyanates or mustard oils. The following reaction schemes may illustrate these methods, described before:

(in this case R =H).

Phenols suitable as starting materials may become apparent from thefollowing table, without however, restricting this invention in any waythereto:

3,313,684 Patented Apr. 11, 1967 f on SOzCHa The new carbamates formedaccording to the process of the invention are distinguished by a goodinsecticidal and acaricidal action while having a low toxic action onwarm blooded animals. In some cases the compounds have also a systemicaction.

The new compounds of the present invention very effectively kill insectslike flies, mites, aphids, etc. They distinguish themselves especiallyby a good contact-insecticidal activity and at the same time by anactivity on eating insects such as caterpillars. The compounds may beused in the same manner as other known insecticides, i.e. in aconcentration from about 0.00001% to about 1%, diluted or extended withsuitable solid or liquid carriers or diluents. Examples of such solidcarriers are talc, chalk, bentonite, clay and the like, as liquidcarriers there may be mentioned water (if necessary with commercialemulsifiers), alcohols, especially lower alcohols such as methanol orethanol, ketones, especially lower ketones such as acetone or methylethyl ketone, liquid hydrocarbons and the like. The new compounds mayfurthermore be used in combination with each other or with knowninsecticides, fertilizers etc.

As an example for the special utility of the inventive compounds theester of the following formula:

has been tested against mosquito larvae, caterpillars and ticks. Aqueoussolutions of the aforementioned compound have been prepared by admixingthem with the same amount of an auxiliary solvent (acetone). Acommercial emulsifier (benzyl hydroxy diphenyl polyglycol ether) isadded in an amount of 20% referred to active ingredient. This premixturethen is diluted with water to the desired concentration. The tests havebeen carried out as follows:

(a) Against mosquito larvae of the type Aedes aegypti: about 20 larvaewere brought into diluted aqueous emulsions prepared as described above.Counting of the dead pests occurred after 24 hours. The followingresults have been obtained: Mosquito larvae were killed completely withsolutions of 0.0001

(b) Against caterpillars: white cabbage has been sprayed drip wet withaqueous emulsions as prepared above in the concentration as indicatedbelow. Caterpillars (of the type diamond back moth, 10 each) have beenplaced on the sprayed leaves of the white cabbage. The living status hasbeen determined after 24 hours and 48 hours. The results are to be seenfrom the following: Caterpillars were killed completed with solutions of0.02%.

Against ticks of the type Boophilus microplus. female ticks each areplaced into mull bags which are brought into a solution prepared asdescribed above while moving them continuously. After 1 minute the mullbags are taken off the active solutions and put into glass dishes inwhich filter paper is placed. The ticks are taken off the mull bags andplaced upon dry filter paper. Evaluation occurred after 24, 48, 72eventually 96 or 120 hours. The following results are obtained: Tickswere killed completely wtih solutions of 0.1%.

The following examples are given for the purpose of illustrating theinvention.

Example 1 ll ems-Q-o-o-rrm 202.6 g. (1 mol) ofp-methylrnercapto-chloroformic acid phenyl ester (B.P. 59 C./0.01 mm.Hg) are dissolved in 700 ml. of toluene. Into this solution anhydrousammonia is introduced while stirring at 0 to +10 C. After completion ofthe reaction, the resulting crystalline product is filtered off withsuction. It is washed with plenty of water. On the other hand, thetoluene solution is evaporated under vacuum. In this way anothercrystalline product is obtained. The two crystalline products arecombined and re-crystallized from anhydrous alcohol. 146 g. ofp-methylmercapto-phenylcarbamate of MP. 141 C. are thus obtained. Yield:80% of the theoretical. On rats per os the ester has a toxicity of 1000mg./kg. Aphids were killed completely with solutions of 0.1%.

By the same way there may be obtained the following compounds:

i mms-Q-o-o-mn Example 2 H ems-Q-w- -NH.orr.

compound:

l oHas@-oo-Nrron1.

Example 3 9.2 g. of finely powdered sodium are dispersed in 100 ml. ofbenzene. To this suspension are added 59 g. of p-methylmercapto-phenoldissolved in 100 ml. of henzene. The suspension is stirred at 3040 C.for 1-2 hours. The sodium salt of p-metl1ylmercapto-phenol has then beenformed. To this suspension is added with further vigorous stirring at 40C. a solution of 108 g. of dimethylcarbamid acid chloride in ml. ofbenzene. When the reaction has subsided, the reaction product is placedinto 400 ml. of ice-water. The benzene solution is separated,de-acidified with a 3% sodium bicarbonate solution and then dried. Inthis Way, 67 g. of p-methylmercapto-phenyl-dimethyl-carbamate of BF.93-94 C./0.01 mm. Hg are obtained. Yield: 79% of the theoretical. The LDtoxicity on rats per os is 1000 mg./kg. Aphids are killed completelywith solutions of 0.1% Systemic action with 0.1% solutions is 100%.

By the same way there may be obtained the following compounds:

79. g. (0.5 mol) of p-methylsulphinylphenol (M.P. 107 C.) are dissolvedin 350 ml. of methyl ethyl ketone. A sodium methylate solutioncontaining 0.5 mol of dissolved sodium is added thereto. Subsequently,60 g. of dimethyl-thiocarbamic acid chloride are added at 40 C. withvigorous stirring. After completion of the reaction, the product isafter-stirred at room temperature for 2 hours. The reaction product isthen placed into 300 ml. of ice-water and worked up as described inExample 1. In this way, 68 g. ofp-methylsulphinyl-phenyl-dimethylcarbamate of M.P. 107 C. are obtained.Yield: 60% of the theoretical. Aphids are killed completely withsolutions of 0.1%. Systemic action with 0.1% solutions is 100%. The LDtoxicity on rats per os is 500 mg./kg.

Example 5 22 g. (0.1 mol) of p-methylmercapto-phenyl-chlorothioformicacid ester (B.P. 72 C./0.01 mm. Hg; M.P. 40 C.) are dissolved in 100 ml.of acetone. This solution is poured with good stirring at -10 C. into amixture of 20 ml. of 25% aqueous ammonia and 50 ml. of acetone. Aftercompletion of the reaction the reaction product is cooled to -10 C. andwater is added carefully as long as crystallisation still occurs. Thecrystalline precipitate is filtered off with suction and recrystallizedfrom benzene. In this way, 9.8 g. ofp-methylmercapto-phenyl-thiocarbamate of MP. 174 C. are obtained. Yield:50% of the theoretical. LD toxicity on rats per os is 1000 per mg./ kg.

Example 6 44 g. (0.2 mol) of p-methylmercapto-phenyl-chlorothioformicacid ester are dissolved in 50 ml. of acetone. This solution is addedwith good stirring at 5 to 0 C. to 50 g. of a 26% aqueous methylaminesolution in 50 ml. of acetone. When the reaction has subsided, thereaction product is placed into 200 ml. of ice-water and cooled to C.The reaction product precipitating in a viscid form is separated anddried on clay. Subsequently the product dried on clay is re-crystallizedfrom benzene. In this way, 16.8 g. ofp-methylmercapto-phenyl-methyl-thiocarbamate of M.P. 161 C. areobtained. Yield: 40% of the theoretical.

By the same way there may be obtained the following compound:

Example 7 I 23 g. of powdered sodium are dissolved in a mixture of 500m1. of benzene and 200 ml. of anhydrous alcohol. 140 g. (1 mol) ofp-methylmercapto-phenol dissolved in 300 ml. of benzene are addedthereto. The alcohol is then evaporated azeotropically with an excess ofbenzene. The residue sodium salt of p-methylmercapto-phenol is dissolvedin 400 ml. of methyl ethyl ketone. 150 g, of dimethyl-triocarbamic acidchloride (M.P. 43 C.) are then added at 70 C. while stirring. Themixture is then heated to 75 C. for 3 hours and worked up in usualmanner. 120 g. of p-methylmercapto-phenyl-dimethylthiocanbamate of B.P.127 C./0.04 mm. Hg, M.P. 93 C., are thus obtained. Yield: 94% of thetheoretical. LD toxicity on rats per os is 1000 mg./ kg.

By the same way there may be obtained the following compound:

Example 8 113 g. (0.5 mol) of the sodium salt of p-methylsulfonylphenolare suspended in 600 ml. of methyl ethyl ketone. 75 g. ofdimethyl-thiocarbamic acid chloride dissolved in 50 ml. of methyl ethylketone are added at 35 C. The mixture is then heated to 60--70 C. forone hour. The reaction product is worked up in the usual manner. 91 g.of p-methylsulphonyl-phenyl-dimethyl-thiocarbamate of M.P 187 C.(redissolved from dioxane) are thus obtained. Yield: 70% of thetheoretical. LD toxicity on rats per os is 1000 mg./kg. 80% of thecaterpillars are killed with solutions of 0.1%

44 g. (0.2 mol) of 4-rnethylmercapto-3-methyl-phenylchloroformic acidester (B.P. 66 C./0.01 mm. Hg) are dissolved in 100 ml. of acetone. Thissolution is added while stirring at 10 C. to 40 m1. of 25% aqueousammonia to which 50 ml. of acetone have been added. When the reactionhas subsided, water is added as long as the re- 6 action productcrystallizes out. The product is then filtered off with suction andrecrystallized from benzene. In this way, 27.6 g. of4-methyl-mercapto-3methyl-phenyl-carbamate of M.P. 144 C. are obtained.Yield: 70% of the theoretical. LD toxicity on rats per os is 1000mg./kg.

Example 10 54 g. (0.25 mol) of 4 methylmercapto 3methylphenyl-chloroformic acid ester are dissolved in ml. of acetone.This solution is added with good stirring at +10 C. to 65 g. of a 26%aqueous methylamine solution. The methylamine solution was dissolved in100 ml. of acetone. When the reaction has subsided, the reaction productis stirred into 300 ml. of ice water. Subsequently the precipitated oilis dissolved in 300 ml. of chloroform. The chloroform solution is shakenseveral times with water, dried over sodium sulfate and then distilled.In this way, 31 g. of 4 methylmercapto 3 methyl phenylmethyl-carbamateof B.P. 111 C./0.01 mm. Hg are obtained. Yield: 59% of the theoretical.Upon prolonged standing, the carbamate solidifies and shows M.P. 81 C.LD toxicity on rats per os is 37.5 mg./kg. Mosquito larvae are killedcompletely with solutions of 0.000-1%. Caterpillars are 100% killed with0.02% solutions. Ticks are completely killed with solutions of 0.1%.

Example 11 47 g. (0.3 mol) of 4 methylmercapt-o 3 methylphenol (M.P. 61C.) are dissolved in 100 ml. of benzene. A sodium methylate solutioncontaining 0.3 mol of dissolved sodium is added thereto. Themethylalcohol is then evaporated azeotropically with an excess ofbenzene. The residual sodium salt is dissolved in 200 ml. of methylethyl ketone and treated with good stirring at 60 C. with 50 g. ofdimethyl-carbamic acid chloride. The mixture is further heated to 70 C.for /2 hour and then worked up in the usual manner. 33.7 g. of 4methylmercapto- 3 methyl phenyl dimethyl carbamate of BF. 121 C./ 0.02mm. Hg are thus obtained. Upon prolonged standing, the carbamatecrystallizes and shows M.P. 70 C. Yield: 50% of the theoretical. LDtoxicity on rats per os is 250 mg./ kg. Mosquito larvae are killedcompletely with solutions of 0.001%. 50% of the ticks are killed withsolutions of 0.05%.

Example 12 0 ll ems-@o-c-nnom lHa 27 g. (0.13 mol) of 4 methylmercapto 3methylphenyl methyl carbamate (M.P. 81 C.) are dissolved in 100 ml. ofmethylalcohol. To the solution are added a few drops of 50% sulphuricacid. 13 ml. of a 35% hydrogen peroxide solution are then added at 40 C.with good stirring. When the reaction has subsided, the product isfurther stirred at room temperature for 5 hours. The reaction product isthen neutralized by the addition of a small amount of calcium carbonate.The salts are filtered off with suction and the solvent and the waterformed are removed under vacuum. In this way, 9 g. of 4 methylsulphinyl3 methyl phenyl methylcarbamate of M.P. 136 C. (from acetone) areobtained. Yield: 30% of the theoretical. LD toxicity on rats per as is10 mg./ kg. Spider-mites and caterpillars are killed completely withsolutions of 0.1%.

7' Example 13 51 g. (0.3 mol) of 4 methylsulphinyl 3 methyl phenol (M.P.123 C.) are dissolved in 250 ml. of ethyl acetate. 42 g. of finelypowdered potassium carbonate are added thereto and the mixture is thenheated to 60 C. while stirring. Subsequently, 50 g. ofdimethyl-carbarnic acid chloride are added thereto and heating iscontinued at 70 C. for a further 2 hours. 200 ml. of chloroform are thenadded and the mixture is cooled to room temperature. The solution iswashed several times with water and then dried over sodium sulphate. Thesolvents are then distilled off under vacuum. The residual pale brownviscous oil solidifies upon prolonged standing. By re-crystallisationfrom benzene there are obtained 29 g. of 4 methylsulphinyl 3 methylphenyl dimethylcarbamate of M.P. 76 C. (from ligroin) are obtained.Yield 40% of theoretical. The LD toxicity on rats per os is 75 mg./ kg.Spider-mites are killed completely with solutions of 0.1%. Ticks are100% killed with 0.6% solutions.

Example 14 56 g. (0.3 mol) of 4 methylsulphonyl 3 methylphenol (M.P. 108C.) are dissolved in 250 ml. of methyl ethyl ketone. Subsequently, 42 g.of anhydrous powdered potassium carbonate are added thereto. 50 g. ofdimethylcarbamic acid chloride are then added dropwise with vigorousstirring at 60 C. and the mixture is heated to 70 C. for an hour. Afterworking up in usual manner, 54 g. of 4 methyl sulphonyl 3 methylphenyldimethyl carbarnate of M.P. 105 C. (from ligroin) are obtained.Yield: 70% of the theoretical. LD toxicity on rats per os is 500 mg./kg.

Example 15 i orns-@oo-N(onol CH3 47 g. (0.3 mol) of 4 methylmercapto 3methylphenol are dissolved in 400 ml. of benzene. A sodium methylatesolution containing 0.3 mol of dissolved sodium is added thereto. Thealcohol is then removed by azeotropic distillation with an excess ofbenzene. The resulting sodium salt is dissolved in 150 ml. of methylethyl ketone. 45 g. of dimethyl-thiocarbamic acid chloride dissolved in100 ml. of methyl ethyl ketone are subsequently added at 45 C. Themixture is heated to 70 C. for one hour and then worked up in usualmanner. 58 g. of 4 methyl mercapto 3 methyl phenyl dimethylthicarbarnateof 13.1. 120 C./0.01 mm. Hg are thus obtained. Yield: 80% of thetheoretical. Upon prolonged standing the carbamate solidifies and showsmelting point 63 C. LD toxicity on rats per os is 100 mg./kg.

Example 16 drous methylamine are added to this solution. When thereaction has subsided, the product is stirred at room 8 temperature fora further 2 hours and then worked up in usual manner. g. of 3 methylmercapto phenylmethyl-earbamate are thus obtained as an orangeyellowwater-insoluble oil. Yield: 76% of the theoretical.

Example 17 om's 70 g. (0.5 mol) of 3 methylmercapto-phenol (B.P. 110C./2 mm. Hg) are dissolved in 400 ml. of benzene. A sodium methylatesolution containing 0.5 mol of dissolved sodium is then added thereto.The methyl alcohol is subsequently distilled off azeotropically with anexcess of benzene. The resulting sodium salt is dissolved in 300 ml. ofmethyl ethyl ketone and treated at 50 C. with good stirring with 60 g.of dimethyl-carbamic acid chloride. The mixture is further heated at 60C. for one hour and then worked up in usual manner. g. of 3-methylmercapto phenyl dimethyl carbamate of B1. 8384 C./0.01 mm. Hg arethus obtained. Yield: 81% of the theoretical.

Example 18 son.

80 g. (0.3 mol) of 1 methylmercapto 2 naphthylchloroformic acid esterare dissolved in 50 ml. of acetone. This solution is added with goodstirring at 10 C. to a solution of 80 g. of a 26% aqueous methylaminesolution in 120 ml. of acetone. When the reaction has subsided, ml. ofwater are stirred in at -10 C. The completely precipitated reactionproduct is then taken up with chloroform. The chloroform layer isseparated and washed wtih water. It is then dried over sodium sulphate.Upon distilling off the chloroform under vacuum, the new carbamateremains as a rapidly solidifying oil. It crystallizes as white needlesshowing M.P. 151 C. Yield: 37 g, corresponding to 50% of thetheoretical. L13 toxicity on rats per os is 750 mg./kg. Aphids arecompletely killed with solutions of 0.1%.

Example 19 SCH;

57 g. (0.3 mol) of 1-methy1mercapto-2-napthol (B.P. 70C./0.01 mm. Hg)are dissolved in 400 ml. of benzene. A sodium methylate solutioncontaining 0.3 mol of dissolved sodium is added thereto. The methylalcohol is subsequently distilled off azeotropically with an excess ofbenzene. The resulting sodium salt is dissolved in 250 ml. of methylethyl ketone. To this solution 35 g. of demethyl-carbamac acid chlorideare added with good stirring. The mixture is subsequently heated to 7075C. for one hour and then worked up in usual manner. 51 g. of 1methylmercapto 2 napthyl-dimethyl-carbamate of M.P. 89C. are thusobtained. Yield: 71% of the theoretical. LD toxicity on rats per os is1000 mg./kg. Aphids are completely killed with solutions of 0.1%.

Example 20 26 g. (0.15 mol) of ethylmercapto-methyl-phenol (B.P. 92C./0.05 mm. Hg) are dissolved in 300 m1. of benzene. A sodium methylatesolution containing 0.15 mol of dis- Example 21 10 Example24.2-etlzylmercapt0-4-metlzylplzenyl- N-methylcarbamate The reaction iscarried out as descn'bed in Example 1. From 16.8 g. (0.1 mol) of2-ethylmercapto-cresol and 6.3 g. (0.11 mol) of methyl-isocyanate areobtained 18.8 g. of carbamate having M.P. 77-80 C. (re-crystallised fromf ligroin). OzHsfi.CHzO-O-N(OH3)2 19 g. (0.09 mol) of4-ethylsulphonyl-methyl-phenol Conc' Aphlds (M.P. 90 C.) are dissolvedin 60 ml. of methyl ethyl ketone. 14 g. of dimethylcarbamic acidchloride are sub- 0,2 1 0 0 1 0 100% sequently added at 70 C. With goodstirring. The mix- 1 8-83 28% 8% g ture is further heated at 70 C. for ashort time and then Worked up in usual manner. 13 g. ofp-ethylsulphonylmethyl-phenyl-dimethyl-carbamate of M.P. 121 C. are thusobtained. Yield: 50% of the theoretical. LD Example25.2-allylmercaptophenyltoxicity on rats per os is 500 mg/kg. Larvae offlies are N-methylcarbamate completely killed with solutions of 0.1%. 0

Example O g H SOzOHa I S-CH2CH=CH2 The reaction is carried out asdescribed in Example 1. O(H3N(CHs)z From 16.6 g. (0.1 mol) ofo-allylmercapto-phenol and 6.3 g. (0.11 mol) of methyl-isocyanate areobtained 13 g. 375 g (015 mol) of 2 hydroxy 5 methyl sulphonyl di ofo-allylmercapto-phenyl-N methylcarbamate. After rephenyl (M.P. 194 c.are dissolved in 150 ml. of methyl crystalhsatlon from hglom 1t melts at66 Q ethyl ketone. To this solution are added 22 g. of finely powderedpotassium carbonate. 20 g. of dimethyl-carbamic acid chloride are thenadded dropwise at 70 C. Cone. Cater- Droso- Aphids Spider Systemic Themixture is heated to 75 C. for one hour and then Plums Phila (Aphlds)worked up in usual manner. 10 g. of the new carbamate T of M.P. 154 C.are thus obtained. Yield: 23% of the 8% iggf? 90% 8g? 90% 90%theoretical. LD toxicity on rats per os is 1000 mg./kg. 0:002 407; :1:III: III: Aphids are completely killed with solutions of 0.1%. 45

Example 23.2-methylmercapto-4-methylphenyl-N- methylcarbamate In asimilar manner the following compounds are obtained: OH3 OgNHOHa 5 H30 0S-OH3 HsCS O-gNHCH3 30.8 g. (0.2 mol) ofZ-methylmercapto-4-methyl-phenol H3O are treated with 13.1 g. (0.23 mol)of methylisocyanate. F On the addition of 3 drops of triethylamine themixture M.P. 121.5

DESTROYED PERCENT Cone. Droso- T. telarius Meal Bean Wax Trombi- Cone.Gall phila moth beetle moth diidae mite begins to react with theevolution of heat. After completion of the reaction, the carbamateseparates out in crystalline form. For purfication, it isIG-CIYStalIlSGd from ligroin. Yield: 40 g.;M.P. 102 C.

Cone. Phaedon- Cater- Droso- Aphids Spider cochleariae pillars philamites Permanent action after spraying: control animal;

0 Piesma quadrata.

DESTROYED PERCENT Cone. Cater- Aphids Grain Fly Mosquito pillars Weevilslarvae larvae i OC-NH. CH1

SCH3-CI'I=CHz DESTROYED PERCENT Cone. Cater- Droso- Aphids SpiderSystemic pillars phila mites (Aphids) Example 26 75.5 parts ofphenyl-N-methylcarbamate and 88.2 parts of4-methylmercapto-3,5-dimethyl-phenol are heated in 200 parts of1,2,4-trichlorobenzene with the addition of 2 parts of sodium acetate to92-95 C. at 8.5 mm. Hg for 2 hours whereby initially only pure phenoldistills oif. Subsequently, the whole trichlorobenzene together with thephenol set free is distilled off at 100-110 C. with the simultaneousdropwise addition of a further 200 g. of 1,2,4-trichlorobenzene, finallypressure of 1 mm. Hg. The residue is stirred into 500 parts of 2 Nsodium hydroxide solution. The precipitated crystals are filtered oilwith suction and Washed with water, until the filtrate runs off neutral.After drying, 65 parts of 4-methylmercapto-3,5-dimethyl-phenyl-N-methylcarbamate of melting point 121 C. areobtained. After acidification with sulphuric acid, extraction withbenzene and distilling off of the benzene, 32 parts of4-methylmercapto-3,S-dimethylphenol are recovered from the filtrate.

Example 27.--0-Pr0pargyl-mercapto-phenyl- N-methyl-carbamare 41 g. (0.25mol) of o-propargyl-mercapto-phenol are suspended in a small amount ofbenzene and reacted with 15.7 g. (0.27 mol) of methyl-isocyanate. Afterthe addition of 1 drop of tri-ethyl-amine the mixture starts reacting.Then the solvent is removed under vacuum and the Example Z8.-o-(c-Chloro-allylmercapto -phenyl- N -methy lcarbamate SCHz-C=CH2 20 g.(0.1 mol) of o-(2-chloro-allyl-mercapto)phenol are suspended in benzeneand reacted with 6.3 g. (0.11 mol) of methyl-isocyanate and 3 drops oftri-ethyl-arnine.

After completion of the reaction, the carbamate is recrystallized fromligroin. Ml. 43.

Cone. Caterpillars D. fabae T. talarius Systemic green resist. D. jabaeWe claim:

1. A method for combating insects which comprises contacting saidinsects with an effective amount of a compound of the following formulaR Reed-(0H2). i OON ll A R1 wherein stands for a member selected fromthe group consisting of NH NH alkyl, N(alkyl) -said alkyl each having 1to 4 carbon atoms-and a 5 to 6 membered heterocyclic radical in whichthe ring members are selected from the group consisting of carbon,nitrogen, oxygen and sulto complete a naphthyl radical and n is a wholenumber from 0 to l.

2. A method for combating insects which comprises contacting saidinsects with an effective amount of a compound of the following formulastands for a member selected from the group consisting of NH NH alkyl,N(alkyl) -said alkyl each having 1 to 4 carbon atoms-and a 5 to 6membered heterocyclic radical in which the ring members are selectedfrom the group consisting of carbon, nitrogen, oxygen and sulfur; A is amember selected from the group consisting of oxygen and sulfur; R is amember selected from the group consisting of alkyl having 1 to 4 carbonatoms, alkenyl having 1 to 4 carbon atoms, 2- chloro-allyl andpropargyl; X is a member selected from the group consisting of S, SO andS0 R is a member selected from the group consisting of hydrogen, loweralkyl and phenyl, R is a member selected from the group consisting ofhydrogen and lower alkyl and n is a whole number from 0 to 1.

3. A method for combating insects which comprises contacting saidinsects with an effective amount of a compound of the following formulawherein stands for a member selected from the group consisting of NH NHalkyl, N alkyl, N(alkyl) said alkyl each having 1 to 4 carbon atomsand a5 to 6 membered heterocyclic radical in which the ring members areselected from the group consisting of carbon, nitrogen, oxygen andsulfur; A is a member selected from the group consisting of oxygen andsulfur; R is a member selected from the group consisting of alkyl having1 to 4 carbon atoms, alkenyl having 1 to 4 carbon atoms, 2-chloro-allyland propar gyl and X is a member selected from the group consisting ofS, SO and S 4. A method for combating insects which comprises contactingsaid insects with an effective amount of a compound of the followingformula wherein alkyl has from 1 to 4 carbon atoms; R and R are eachlower alkyl and R is alkyl having from 1 to 4 carbon atoms.

5. A method for combating insects which comprises contacting saidinsects with an efiective amount of a compound of the following formulawherein alkyl and R are each alkyl having from 1 to 4 carbon atoms.

7. A method for combating insects which comprises contacting saidinsects with an effective amount of a compound of the following formulaS II 8. A method for combating insects which comprises contacting saidinsects with an effective amount of a compound of the following formulaSCHa 10. A method for combating insects which comprises contacting saidinsects with an effective amount of a compound of the follo vn'ngformula S-CHa 11. A method for combating insects which comprisescontacting said insects with an effective amount of a compound of thefollowing formula CH: H.C. O l NH .H.

12. The compound of the following formula:

0 E1468 0- H NHCHs References Cited by the Examiner UNITED STATESPATENTS 2,776,197 1/1957 Gysin et al. 7l2.4 3,206,502 9/1965 Heiss etal. 260479 FOREIGN PATENTS 554,576 3/1958 Canada. 1,275,658 10/1961France. 1,142,599 1/1963 Germany. 1,147,572 4/1963 Germany. 1,148,1075/1963 Germany. 1,162,352 2/1964 Germany.

912,895 12/1962 Great Britain.

OTHER REFERENCES Kolbezen et al., Journal of Agricultural and FoodChemistry, 2: 864-870 (1954).

German application G15250Na/451, filed October 1956.

ELBERT L. ROBERTS, Primary Examiner. LEWIS GOTIS, Examiner.

S. K. ROSE, Assistant Examiner.

1. A METHOD FOR COMBATING INSECTS WHICH COMPRISES CONTACTING SAIDINSECTS WITH AN EFFECTIVE AMOUNT OF A COMPOUND OF THE FOLLOWING FORMULA12. THE COMPOUND OF THE FOLLOWING FORMULA:H3C-S-(2,6-DI(H3C-)-1,4-PHENYLENE)-OOC-NH-CH3